Heat Capacities and Thermodynamic Properties of Ammonium Nitrate
Heat Capacities and Thermodynamic Properties of Ammonium Nitrate
Heat Capacities and Thermodynamic Properties of Ammonium Nitrate
stable and metastable phases by use of adiabatic- and conduction-type calorimeters. The phase
transformations between stable phases; i. e., V-IV, IV-III, III-II and II-I, and the met-
astable one between IV and II, were all found to be of first-order type. The direct transition
between V and II, which is only realized for the sample treated with a minute amount of sur-
face active agent, was ascertained to be typical higher-order type. Heat and entropy of transi-
tion of five kinds of transitions were determined. These results conclude that the heat capacity
data by Stephenson et al. at low temperature region are much more reliable than the recent
values by Eichenauer et al. The possibility of the existence of the seventh phase below 156°K
Since the discovery of anomalous peak in specific On the other hand, mainly Finnish workers
heat curve of ammonium chloride by Simon et al. performed systematic calorimetric studies of various
in 1927, there have been accumulated so many kinds of metal nitrate crystals which also exhibit
results with calorimetric investigations on various similar kind of phase transitions due to the disor-
kinds of ammonium salts. These informations dered orientation of nitrate ion. A review article
together with a variety of physical properties ob- on the relationship between the entropy of transi-
tained have been attracting many people to un- tion and crystal structure change on these com-
derstand this effect more in detail from theoretical pounds has been published quite recently by Newns
as well as experimental points of view. and Staveley.1)
The present material, ammonium nitrate com-
†1 Read before the 19th Annual Meeting of the
posed of these two, ammonium and nitrate ions, is
Chemical Society of Japan, Yokohama,1966.
†2 Present address:Department of Chemical
Engineering, Faculty of Engineering, Kagoshima 1) D. M. Newns and L. A. K. Staveley, Chem.
University, Kagoshima. Revs., 66, 267 (1966).
1834 M. NAGATANI, T. SEIYAMA, M. SAKIYAMA, H. SUGA and S. SEKI [Vol. 40, No. 8
still a very interesting substance to study in these ing considerably at higher temperature region from
respects and indeed demonstrates many phase the data by Stephenson et al.
transitions of rather complex nature. Already in In the present study we have measured the specific
1932, three papers were published independently, heat from 15 to 410°K with focusing our special
with regard to the crystal structure and thermal attention on the following few points: i) To re-
properties, by Hendricks, Posnjak and Kracek,2) examine the reliability of the recent data of specific
West,3) and by Grenshaw and Ritter.4) Since then, heat by Stephenson et al. and Eichenauer et al.,
these studies interested many workers from the ii) To check the possibility of presence of the seventh
point of above-mentioned order-disorder orienta- modification, iii) To establish the free energy rela-
tional rearrangement of ammonium and nitrate tionship between all conditions governing the direct
ions in the lattice. transformation from phase II to V which was first
Through the effort of these investigations, this suggested by Amoros et al.13) from structural view
crystal is known to exist in at least five solid phases point and later really found by one of the present
at ordinary pressures. These modifications with authors14) by treating the sample with minute
the pertinent data on crystal structure and transi- amount of surface active agent, and iv) To esta-
tion points are given in Table 1. blish the reliable numerical data of enthalpies
A sixth phase is reported to be stable above 442°K of each transitions.
at pressures higher than 9000 kg/cm2 by Bridgman.8) The last point concerns with the differential
There remains, however, still seemingly somewhat thermal analysis method in which almost all
contradicting or unsolved problems on a possibility workers check the availability of their instruments
of the existence of the seventh modification at lower with the detection of the phase transitions of this
temperature, suggested by spectroscopic, thermal or compound, notwithstanding that there is no com-
other studies by Crenshaw and Ritter,4) Jaffrey,9) plete set of their reliable data.
Vol'fkovich et al.,10) Theoret and Sandorfy11) and
others.
Experimental
As to the specific heat itself, it has been believed
that the precise measurement by Stephenson et al.5) Materials. A special, reagent-grade ammonium
established the conclusive data below 315°K. nitrate (Nakarai Chem. Ind. Ltd.) was recrystallized
Quite recently, however, Eichenauer and twice from ethyl alcohol (special-grade, Wak&Chem.
Liebscher12) published a new result which is deviat- Ind. Ltd.), and then dried under high vacuum (10-6
mmHg) for 10 hr. This sample was then powdered.
This drying and powdering procedures were repeated
2) S. B. Hendricks, E. Posnjak and P. C. Kracek. three times, one after the other, in order to remove
J. Am. Chem. Soc., 54, 2766 (1932).
C 3) completely the occluded mother liquor.
. W. West, ibid., 54, 2256 (1932). A specimen used for the measurement of the specific
4) J. L. Crenshaw and I. Ritter, Z. physik. Chem.,
B 16, 143 (1932). heat of metastable phase transition between phase V
5) C. C. Stephenson, D. R. Bentz and D. A. and II was prepared by adding a small amount of
Stevenson, J. Am. Chem. Soc., 77, 2161 (1955). additive to the original specimen, and this is referred
6) D. H. Everet and A. E. P. Watson, Trabajos to as"specimen-add'hereafter.† The additive used
reunion intern. reattiaidad solidos,3°, Madrid,1956,1, for the present work is octadecylamine acetate, the
301-319. amount of which is about 0.2 wt%. The additive
7) V. Hovi, J. Poyhonen and P. Paalassalo, Ann. was prepared by neutralization of octadecylamine
Acad. Sci. Fennicae, Ser. A VI, 42, 3 (1960).
8) P. W. Bridgman, Proc. Am. Acad. Arts Sci., 51, (Wako Chem. Ind. Ltd.) with acetic acid, according
605 (1916). to the ordinary method. The procedure taken for
9) J. Jaffrey, Compt. rend., 224, 1346 (1947).
10) S. I. Vol'fkovich, S. M. Rubinchik and V. M.
Kpzhin, Izvest. Akad. Nauk. S. S. S. R., Otdel. Khim. 13) J.L. Amoros Portoles and R. L. Banerjee,
11) A. Theoret and C. Sandorfy, Can. J. Chem., 14) M.Nagatani, Kogyo Kagaku Zasshi(J. Chem, Sot.
TABLE 2. (Continued)
addition was as follows: The additive was dissolved using the benzoic acid as a reference of heat capacity.
into benzene (special-grade, Wako Chem. Ind. Ltd.), The weight of samples employed for the conduction-
and pure ammonium nitrate was soaked into this solu- type calorimeter was 5.1536 g or 0.06438 mol for pure
tion. After vigorous stirring of the soaked specimen specimen and 4.8130 g or 0.06013 mol for specimen-
in the solution, the liquid benzene was evaporated com- add, respectively. The heating or cooling rate was.
0.2-0.3℃/min, except the transition regions. In
pletely at room temperature. For introducing the
specimen into the calorimeter cell a vacuum-type dry the operated temperature region, the experimental
box filled with dry nitrogen gas was employed for error of the conduction calorimeter is believed to be less,
avoiding the humidity from the sample. than±0.5%.
15) H. Suga and S. Seki, This Bulletin, 38, 1000 Fig. 1. The heat capacity of NH4NO3 between
170 and 260°K.
(1965). S16)
. Seki, M. Momotani, K. Nakatsu and T. ○ Series 3 ● Series 5 ● Series 6
Oshima, ibid., 28, 411 (1955). ▲ Stephenson et al.5)
17) W. T. Ziegler and C. E. Messer, J. Am. Chem. △ Eichenauer and Liebscher12)
Soc., 63, 2694 (1941).
Temperature scale at the top is for the upper
18) W. T. Berg and J. A. Morrison, Proc. Roy. Soc.
curves above the dotted line.
(London), A242, 467 (1957).
August, 1967] Heat Capacities and Thermodynamic Properties of Ammonium Nitrate Crystal 1837
chronological order. They are the ratios of the in- TABLE 3. SELECTED VALUES FOR HEAT
crease in enthalpy, ⊿H, to the rise in temperature, CAPACITY OF NH4NO3
⊿T. Each vaiue of Tav in the table is the ari-
to be 273.15°K.
(2)
Where Cp (est.) stands for the heat capacity
of phase V, V* or II; Cp(run 1), Cp(run 3), the-
observed heat capacity in each run; and the value
0.430, the fraction which undergoes the transi-
tion V-V*-II in run 3. This value was de-
termined by comparison of the apparent heats
of transition IV-II in run I and 3, and equating its
Fig. 4. Metastable phase transitions IV-II and to [1-⊿H(run 3)/⊿H(run 1)], where ⊿H(run 1)
V-V*-II appeared in NH4NO3-add. and ⊿H(run 3)were 1860 and 1060(⊿H(run 5)=
Peak 1: V-V * Peak 2: V *-II
1270) J/mol, respectively.
Peak 3: IV-II
The heat capacities determined by this proce-
(3) The measurements with specimen-add were dure are listed in Table 4. The estimation with
repeated three times by heating and succesive the data in run 5 instead of those in run 3 is also
cooling procedures in the temperature range from possible, but this procedure was abandoned, since
275 to 340°K. All the features obtained by this
the results are rather uncertain due to the smaller
fraction of the transition V-V*-II part.
process of measurement near the phase transition
were reproduced in Fig. 4.
† The appearence of the metastable V*phase
In the first heating (run 1) of the virgin specimen, cited here were originally confirmed by DTA and X-
transition IV→II occurs and in the succcssive ray methods (see Ref. 14).
August, 1967] Heat Capacities and Thermodynamic Properties of Ammonium Nitrate Crystal 1839
TABLE 4. SELECTED VALUES FOR HEAT TABLE 5. TEMPERATURES, ENTHALPIES AND ENTROPIES
380°K.
Thermodynamic Properties of
Ammonium Nitrate
TABLE 6. THERMODYNAMIC PROPERTIES OF NH4NO3 60 and 320°K, and±0.5% above 320°K. The
(STABLE PHASE other thermodynamic quantities in the tables were
(in J/(mol・deg K)) derived from the smoothed heat capacity curves
and the heat of transition data of the stable tran-
sitions in Table 5.
Table 7 is for the metastable states of phase IV
(4)
Discussion
Gibbs energy function of phase II in Table 7 are 19) J. Whetstone, Acta Cryst., 7, 697 (1954).
20) R. N. Brown and A. C. McLaren, Proc. Roy..
larger than those in Table 8 by -0.012, 0.02 and Soc. (London), A266, 329 (1962).
August, 1967] Heat Capacities and Thesmodynamic Properties of Ammonium Nitrate Crystal 1843
Fig. 8. Gibbs energy vs. temperature curves of NH4NO3. In this figure, the Gibbs energies
are standardized at the state o」phase V at 256.2°K, as follows;
G=H°-H°256.2(V)-T(S°-S°256.2(V))
As there is no description about the sample they heat curve at around 156°K(-117℃)found by
used, we cannot understand the reason why the us may be looked upon as a corresponding one.
heat capacity data obtained by Eichenauer and The slightness in its effect may be consisting with
Liebscher12) are significantly lower than Ste- the facts that there is no noticeable change in the
phenson's and our data for phases IV and V in its second moment of broad line NMR spectra by
higher temperature region. But, it may be one of Goodwin and Whetstone,22) Gutowsky et al.23)
the possibilities that their sample (V) contains some and by Richards et al.24) The only inconsistent
amount of remained phase III or IV. report against this view is the transition point at
around -160℃ by _Taffrey.9) But there is no
(2) Possibility of the Existence of Phase
VII. As is already described there is a number description about the specific heat data, so we can
of papers which prove the existence of the seventh not check the reliability of his measurement.
phase. But the evidences are not always so definite Anyhow, it seems much desirable to check this
and some of them are contradicting with each other. transition point by using some other techniques.
The transition point at about -60℃ reported by (3) Nature of Phase Transition between
Crenshaw and Ritter,4) and by Jaffrey9) was not V, V* and II. The transition between V and II,
detected by the specific heat measurements by which really consists of two steps, shows some-
Stephenson et al., Eichenauer et al. and by us. what different behaviors from the others. As is
The only seemingly supporting result is the infrared shown in Figs. 4 and 5, the specific heat curve
study by Theoret and Sandorfy.11) They suggest, shows a conspicuous maximum and the Gibbs
however, that this transition point is not corre- energy curve shows no intersection with each
sponding to the transition between IV and VII. other. These facts indicate that this phase transi-
Vol'fkovich et al.,10) who first substantiated tion is of higher order nature. Amoros et al.25)
existence of phase VII, observed this phase at have carried out the complete crystal structure
about -170℃, but they did not report the transi- analysis of phase V at lower temperature which
tion point between V and VII. Judging from these is given in Fig. 9. According to their result,
findings the true transition point between V and the molecular packing quite resembles that of
VII will lie between -60℃ and -170℃. This phase 1113,16)which is shown in Fig. 10. They
expectation seems to be compatible with the ob- suggested that the phase II is a kind of vibra-
servation by Newman and Halford.21) They con-
cluded the significant change in the infrared spectra 22) T. H. Goodwin and J. Whetstone, J. Chem.
Soc., 1947, 1455.
must occur at temperature intermediate between 23) H. S. Gutowsky and G. E. Pake, J. Chem. Phys.
-65 and -160℃ . Taking these consistent ob- 16, 1164 (1948).
servations into account, the small hump in specific 24) R. E. Richards and T. Schaefer, Trans. Faraday
Soc., 57, 210 (1961).
25) J. L. Amoros Portoles, F. Arrese and M. L.
21) R. Newman and R. S. Halford, J. Chem. Phys., Canut, Z. Krist., 117, 91 (1962).
18, 1291 (1950). 26) Y. Shinnaka, J. Phys. Soc. Japan, 11, 393 (1956).
1844 M. NAGATANI, T. SEIYAMA, M. SAKIYAMA, H. SUGA and S. SEKI [Vol. 40, No. 8
Summary